KR20010033099A - Antistatic elastic polyurethane fiber and material for producing the same - Google Patents

Abstract

Inorganic salts are produced in sulfonic acid metal salts of hydrocarbons, sulfuric acid metal salts of hydrocarbons and metal phosphate salts of hydrocarbons. If the inorganic salt is contained and added to the polymer for producing polyurethane fibers as an antistatic component, the yarn breaks or packs due to the inorganic salt during spinning. In addition, the antistatic component has high hygroscopicity and contains a small amount of water. When such an antistatic component is added during the polymerization of the polyurethane, the alcohol component and the water react with the isocyanate to cause a decrease in the degree of polymerization and the formation of oligomers, and elongation and strength are lowered even if the polyurethane is spun. The raw material for polyurethane elastic fiber of the present invention is mixed with at least one kind of 5 ~ 95% by weight of the above-mentioned antistatic component with 95 ~ 5% by weight of the raw material for producing elastic fibers containing no isocyanate, and solves the above problems. .

Description

Antistatic Polyurethane Elastic Fiber and Raw Material for Manufacturing the Same {ANTISTATIC ELASTIC POLYURETHANE FIBER AND MATERIAL FOR PRODUCING THE SAME}

Japanese Patent Application Laid-Open No. 7-166426 discloses an elastic yarn containing 0.1 to 5% by weight of sulfonic acid metal salt of a hydrocarbon having 12 to 22 carbon atoms and having an oil agent containing dimethylsiloxane on the yarn surface.

Japanese Patent Application Laid-Open No. Hei 1-90258 discloses a method of producing an antistatic polyurethane foamed molded product by dissolving an organic sulfonate phosphonium salt in a polyurethane stock solution in advance, followed by a polyurethane production reaction. have.

Sulfonate metal salts of hydrocarbons, sulfuric acid metal salts of hydrocarbons, or metal salts of phosphates of hydrocarbons produce inorganic salts in the production process. When these salts are used in the polymer stock solution for fiber production containing the above inorganic salts, the yarns break or pack clogging occurs during spinning due to the inorganic salts that do not dissolve in the polymer stock solution. For this reason, it is necessary to refine | purify the above sulfonic acid metal salt etc. using organic solvents, such as alcohol, beforehand. In general, the sulfonic acid metal salts and the like above have high hygroscopicity and contain a small amount of water. Therefore, in the case where the sulfonic acid metal salt as described above is 100% pure, the alcohol component and moisture remain by 1% by weight or more even after vacuum drying. When such an alcohol component or a sulfonic acid metal salt containing water is added during the polymerization of the polyurethane, the alcohol component and the moisture react with the isocyanate to produce a decrease in the degree of polymerization or oligomers. There was a problem of deterioration.

Disclosure of the Invention

It is therefore an object of the present invention to provide a raw material containing sulfonate metal salts of hydrocarbons and the like for producing antistatic polyurethane elastic fibers containing sulfonate metal salts of hydrocarbons as antistatic agents.

Another object of the present invention is to prevent the presence of alcohol or water that reacts with isocyanate to inhibit the polyurethane production reaction at the time of carrying out the polyurethane production reaction, the antistatic poly that can suppress the inhibition reaction of alcohol and water as much as possible It is to provide a raw material for producing urethane.

It is still another object of the present invention to provide a raw material for producing an antistatic polyurethane elastic fiber containing a sulfonic acid metal salt of hydrocarbon as an antistatic agent having a low inorganic salt content.

Still another object of the present invention is to provide an antistatic polyurethane elastic fiber having sufficient strength and elongation as an elastic fiber.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are firstly selected from the group consisting of sulfonates of hydrocarbons of 8 to 30 carbon atoms, sulfates of hydrocarbons of 8 to 30 carbon atoms and phosphates of hydrocarbons of 8 to 50 carbon atoms. 5 to 95 parts by weight of one salt and

It is achieved by the raw material for antistatic polyurethane elastic fiber manufacture which consists of a mixture of 95-5 weight part of raw materials for polyurethane elastic fiber manufacture other than organic isocyanate (the total of both shall be 100 weight part).

The above objects and advantages of the present invention are secondly achieved by an antistatic polyurethane elastic fiber containing from 0.1 to 10% by weight of the salt and from 0.1 to 10% by weight of lubricant and having a strength of at least 1 g / de and an elongation of at least 400%.

The present invention relates to an antistatic polyurethane elastic fiber and a raw material for producing the same.

1 is an explanatory diagram of a device for measuring knitting tension.

Preferred Embodiments of the Invention

In the present invention, the raw material means a raw material for producing an antistatic polyurethane elastic fiber. In the antistatic polyurethane elastic fibers, polyurethane elastic fibers are long-chain glycols such as organic diisocyanate, polytetramethylene glycol, polyesterdiol and short-chain difunctional such as 1,2-propylenediamine and 1,4-butanediol. The polyurethane fiber obtained from a compound etc. as a starting material is meant. Such fibers can be produced by spinning a spinning stock solution prepared by dissolving polyurethane in a spinning solvent by a method known per se.

Salts used as antistatic agents in the raw materials of the present invention are sulfonates of hydrocarbons of 8 to 30 carbon atoms, sulfates of hydrocarbons of 8 to 30 carbon atoms, and phosphates of hydrocarbons of 8 to 50 carbon atoms. These can be used together 1 type or 2 types or more.

Examples of the sulfonate of a hydrocarbon having 8 to 30 carbon atoms include, for example, an alkanesulfonic acid K salt having an average carbon number of 15.5, an alkanesulfonic acid salt of an average carbon number of 10.5, a dodecyl benzene sulfonic acid Na salt, and a dibutylnaphthalin sulfonic acid Na salt. , Toluene sulfonic acid tetrabutylphosphonium salt, toluene sulfonic acid trioctylmethylammonium salt, polyoxyethylene lauryl ether propane sulfonic acid Na salt, nonyl phenyl ether propane sulfonic acid K salt and petroleum sulfonic acid Na salt, etc. are mentioned as a preferable thing. have.

Examples of the sulfate of the hydrocarbon having 8 to 30 carbon atoms include octyl sulfate Na salt, stearyl sulfate K salt, cetyl sulfate tetrabutyl phosphonium salt, polyoxyethylene lauryl ether sulfate Na salt, polyoxyethylene nonylphenyl ether sulfate K Salts, sulfated castor oil Li salts and methylsulfinosulfonate sulfate salts and the like can be cited as preferred ones.

Moreover, as a phosphate of C6-C50 hydrocarbon, mono, dilauryl phosphate Na salt, mono distearyl phosphate K salt, mono, dipolyoxyethylene lauryl ether phosphate Na salt, mono, dipolyoxyethylene nonyl phenyl ether phosphate K salt, monodibutyl phosphate Na salt, etc. are mentioned as a preferable thing.

It is necessary that the said antistatic component used for this invention does not have group which has reactivity with organic isocyanate, and a metal salt is preferable at the point of antistatic effect.

In the present invention, the antistatic agent is contained in the polyurethane elastic fiber 0.1 to 10% by weight, preferably 0.3 to 3% by weight. Outside this range, the antistatic effect is insufficient, or the elongation is reduced.

Moreover, the inorganic content of an antistatic agent becomes like this. Preferably it is 0.5 weight% or less, More preferably, it is 0.1 weight% or less. If the inorganic content is high, the thread may be broken or the radiation pack may be blocked.

The raw material of the present invention contains raw materials for producing polyurethane elastic fibers other than salts such as sulfonate salts and organic diisocyanates. The ratio is preferably 5 to 95 parts by weight of the former salt and 95 to 5 parts by weight of the latter raw material when the total of both is 100 parts by weight.

As a raw material for polyurethane elastic fiber manufacture of the latter, long-chain glycols, a short-chain bifunctional compound, a spinning solvent, a lubricating agent, antioxidant, an ultraviolet absorber, etc. for polyurethane manufacture are mentioned, for example. These can be used together by 1 type, or 2 or more types. Of these, long chain glycols, spinning solvents and lubricants are preferred.

Examples of the long chain glycols for producing polyurethanes include polytetramethylene glycol, polyesterdiol, polypropylene glycol, and polyethylene glycol. Among these, polytetramethylene glycol and polyesterdiol are preferable.

In addition, as a short-chain bifunctional compound for polyurethane manufacture, for example, succinic acid, adipic acid, ethylene glycol, propylene glycol, 1,4-butanediol, hexanediol, hydrazine, 1,2-propylenediamine, 1,4-butylene Diamine, 1,6-hexamethylenediamine, m-xylenediamine, and the like.

In addition, examples of the spinning solvent include dimethylformamide, N, N'-dimethylacetamide, N, N, N ', N'-tetramethylurea, N-methylpyrrolidone and dimethyl sulfoxide. Of these, N, N-dimethylformamide and N, N-dimethylacetamide are preferable.

Examples of the lubricant include saturated higher fatty acid metal salts such as stearic acid Mg, modified silicones such as amino modified silicones, alkylether modified silicones, and polyether modified silicones, and higher fatty acid amides. Among these, bisamides, such as modified silicone and ethylene bis stearic acid amide, are preferable.

The antistatic polyurethane elastic fiber of this invention can be manufactured suitably by using the said material of this invention. That is, the raw material of the present invention is mixed with a raw material for producing polyurethane elastic fibers other than organic diisocyanate, and then dried under reduced pressure, for example, by a known means thereof, before being combined with organic diisocyanate, and contained therein. Water and alcohol can be easily removed to low levels. The raw material of the present invention preferably contains only up to 0.5% by weight of water and up to 0.5% by weight of alcohol, more preferably contains up to 0.1% by weight of water and only up to 0.1% by weight of alcohol.

When manufacturing a polyurethane elastic fiber using the raw material of this invention, the raw material of this invention can be manufactured by a well-known method by treating it like a raw material for polyurethane elastic fiber manufacture other than organic diisocyanate. have.

Thus, according to the present invention, an antistatic polyurethane elastic fiber containing 0.1 to 10% by weight of the salt as an antistatic agent and 0.1 to 10% by weight of a lubricant and having an intensity of 1 g / de or more and an elongation of 400% or more is suitably provided. do.

According to the present invention, since the content of the raw material of the present invention is low in content of water, alcohol or inorganic salts, it does not cause a decrease in the degree of polymerization or formation of oligomers, and does not cause the generation of scum without reducing the elongation of the fibers. The fiber of the present invention is preferably produced. In addition, since the antistatic component is dispersed in the raw material in advance, the mixing of the antistatic component in the spinning stock solution proceeds smoothly and uniformly, so that the antistatic property of the fiber of the present invention is even and uniform.

This invention is demonstrated concretely by the following Example.

Example 1

Monodipolyoxyethylene lauryl ether phosphoric acid was neutralized with 50% KOH aqueous solution to prepare a 50% polytetramethylene glycol solution thereof. The solution was warmed to 130 ° C. and water was removed at −700 mmHg to obtain a polytetramethene glycol solution of monodipolyoxyethylene lauryl ether phosphate K of 200 ppm of water and 0.05% of inorganic salt (hereinafter referred to as additive a). .

Example 2

Crude octyl sulfate Na containing sodium sulfate was dissolved in ethanol to precipitate sodium sulfate, followed by filtration. The filtrate was dried to obtain a powder of 0.05% by weight of ethanol component, 0.02% by weight of water and 0.01% by weight of inorganic salt. This was then used as a 10% by weight solution of N, N-dimethylacetamide (DMAc) (referred to as additive b).

Example 3

The crude dodecylbenzenesulfonic acid containing sulfuric acid was neutralized with NaOH / methanol, and sodium sulfate was precipitated and removed to obtain a 70% dodecylbenzenesulfonic acid Na / methanol solution. 67 parts by weight of polyether modified silicone (PO / E0 = 40/60, viscosity 3000cst / 25 ° C) was added to 47 parts by weight of this solution, warmed to 130 ° C, methanol was removed at -700 mmHg, water content of 0.06% by weight, methanol 0.05 A solution of% by weight and 0.01% by weight of inorganic salt was prepared (hereinafter referred to as additive c).

Example 4

Crude alkanesulfonic acid Na containing sodium sulfate having an average carbon number of 15.5 was dissolved in methanol to precipitate sodium sulfate, followed by filtration. Then, ethylenebisstearic acid amide was added 20% by weight relative to alkane sulfonic acid Na having an average carbon number of 15.5, up to 130 ° C. After heating up, it dried under vacuum of -700mmHg, and prepared the solution of 0.4 weight% of water, 0.1 weight% of methanol components, and 0.02 weight% of inorganic salts (henceforth additive d).

Example 5

98 parts by weight of polytetramethylene glycol having a number average molecular weight of 1500, 2 parts by weight of additive a, and 33 parts by weight of 4,4'-diphenylmethane diisocyanate were reacted at 70 ° C, followed by addition of 266 parts by weight of N, N-dimethylacetamide. The reaction mixture was dissolved while cooling. When the internal temperature reached 5 ° C, 5 parts by weight of 1,2-diaminopropane was dissolved in 184 parts by weight of N, N-dimethylacetamide and 10 parts by weight of an additive a were added. The spinning stock solution thus obtained was supplied to a spinning nozzle having four pores, extruded in a hot air and spun at 200 m / min while evaporating the solvent, and 5 weights of (1/1) mixed oil of dimethylsilicone 10cst and mineral oil 60 seconds was used. After winding, it was wound up (40de). The properties of the obtained fiber are shown in Table 1.

Example 6

100 parts by weight of polytetramethylene glycol having a number average molecular weight of 2000 and 25 parts by weight of 4,4'-diphenylmethane diisocyanate were reacted at 70 DEG C, followed by addition of 250 parts by weight of N, N'-dimethylacetamide to the reaction mixture while cooling. Was dissolved. When the internal temperature reached 5 ° C, 3.7 parts by weight of 1,2-diaminopropane was dissolved in 183 parts by weight of N, N'-dimethylacetamide and 10 parts by weight of the additive b were added. The spinning stock solution thus obtained was spun in the same manner as in Example 5. The properties of the obtained fiber are shown in Table 1.

Example 7

In Example 6, instead of 10 parts by weight of the additive b, 2 parts by weight of the additive c was added and spinning was performed in the same manner. The properties of the obtained fiber are shown in Table 1.

Example 8

37.5 parts by weight of 4,4'-diphenylmethane diisocyanate and 2 parts by weight of the additive d were reacted at 100 ° C with 100 parts by weight of polymethylpentanediol adipate having a number average molecular weight of 2000 and 9 parts by weight of 1,4-butanediol. The obtained reactant was taken out from the kneader, extruded from four pores at 200 ° C by an extruder, spun at 200 m / min, and wound up after giving 5 parts by weight of a mixed oil of dimethylsilicone 10 cst / mineral oil 60 seconds (1/1) (40de). ). The properties of the obtained fiber are shown in Table 1.

Example 9

The spinning was carried out in the same manner as in Example 8 except that the additive d was 0.5 part by weight. The properties of the obtained fiber are shown in Table 1.

Example 10

Instead of 10 parts by weight of additive b in Example 6, 0.5 parts by weight of additive c was added and spun in the same manner. The properties of the obtained fiber are shown in Table 1.

Comparative Example 1

In Example 7, a commercially available alkanesulfonate having an average carbon number of 14.5 (inorganic salt content of 4% by weight and water content of 2% by weight) was used in place of the additive c. As a result, the pack pressure increased during spinning, which allowed to spin for only 5 hours. There was no. The obtained elastic yarn could not be used as an elastic yarn at 270% elongation and 0.5 g / de in strength.

Comparative Example 2

In Example 1, spinning was performed without using an additive. The properties of the obtained fiber are shown in Table 1.

Organizing Tension:

1 will be described. The urethane yarn 2 pulled out lengthwise from the cheese 1 is passed through a roller 4 and a single needle 5 via a compensator 3 and attached to the U gauge 6. It connects to the speedometer 8 and the winding roller 9 via (7). The speedometer 8 is wound at a constant speed (for example, 10 m / min, 100 m / min) by a winding roller, and the tension variation at that time is measured by the U gauge 6, and the friction between fibers / eccentrics ( g) is measured.

It measured by setting a collector potential measuring instrument (KS-525; made in spring and summer) 1 cm away from the electrostatic U gauge.

Specific resistance: It measured using FIBER TESTER (TYPE MR-2010) (made by DEMPA IND Co.LTD).

Test No Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 2 Single Growth Force (g) 10m / min 100m / min 2025 2127 2023 2025 2125 2024 2025 Static electricity (kv) 10m / min 100m / min 0.10.2 0.10.2 0.10.1 0.20.3 0.30.3 0.10.2 0.52.0 Specific resistance (Ωcm) 2 × 10 ⁸ 3 × 10 ⁸ 1 × 10 ⁸ 4 × 10 ⁸ 5 × 10 ⁸ 2 × 10 ⁸ 4 × 10 ¹¹ Strength (g / de) 2.3 2.6 2.4 2.3 2.0 2.4 2.3 Elongation (%) 590 620 610 560 570 610 580

By using the raw material of the present invention, it is possible to suppress the generation of static electricity during covering or beaming of the elastic yarn while maintaining good practical performance (elongation of 400% or more and strength of 1 g / de or more). Trouble can be reduced.

Claims (7)

5 to 95 parts by weight of at least one salt selected from the group consisting of sulfonates of hydrocarbons of 8 to 30 carbon atoms, sulfates of hydrocarbons of 8 to 30 carbon atoms, and phosphates of hydrocarbons of 8 to 50 carbon atoms; and A raw material for producing an antistatic polyurethane elastic fiber, which is a mixture of 95 to 5 parts by weight of raw materials for producing polyurethane elastic fibers other than organic isocyanate (total amount thereof is 100 parts by weight). The method of claim 1, A raw material for producing an antistatic polyurethane elastic fiber, wherein the raw material for producing polyurethane elastic fibers is selected from the group consisting of long chain glycols, spinning solvents, and lubricants for producing polyurethane. The method of claim 1, A raw material for producing an antistatic polyurethane elastic fiber, wherein the long chain glycols for producing polyurethane are polytetramethylene glycol or polyesterdiol. The method of claim 1, A raw material for producing an antistatic polyurethane elastic fiber, wherein the spinning solvent is N, N-dimethylformamide or N, N-dimethylacetamide. The method of claim 1, A raw material for producing an antistatic polyurethane elastic fiber whose lubricant is bisamide or modified silicone. The method of claim 1, A raw material for producing an antistatic polyurethane elastic fiber, wherein the salt contains only an inorganic salt up to 0.5% by weight. An antistatic polyurethane elastic fiber containing 0.1 to 10% by weight of the salt and 0.1 to 10% by weight of lubricant, and having a strength of 1 g / de or more and an elongation of 400% or more.